Neutralization process



Oct. 7, 1958 H. D. L YoNs NEUTRALIZATION PROCESS Filed .June 6, 1955 DE-ACID'IFIED mum WASTE) WATER IN VEN TOR.

H. D. LYONS ATTORNEYS niteci States Patent 'a NEUTRALIZATION PROCESS Harold D. Lyons, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Application June 6, 1955, Serial No. 513,524

11 Claims. (Cl. 260-586) This invention relates to the neutralization of liquids. In one aspect this invention relates to contacting a liquid to be neutralized with a neutralizing material and simultaneously revivifying said neutralizing material. In another aspect this invention relates to flowing a stream of liquid through a bed of neutralizing material and simultaneously flowing a stream of water through said bed countercurrent to said stream of liquid.

The problem of neutralizing acid or base containing liquids is a problem which must be faced in many industries wherein liquids are treated with acids or bases or an acid or base is produced as a by-product in a process wherein the main product is a liquid. For example, in the petroleum industry hydrocarbons are frequently treated with acid to improve the color or other properties thereof and frequently residual acid from said treatment must be removed from the hydrocarbons. In alkylation processes employing an acid catalyst, such as hydrouoric acid or sulfuric acid, the efuent from the reaction zone must be neutralized. Another example is when an acid catalyst is used in the polymerization of the hydrocarbons. Still Vanother example is the neutralization of the acids formed as a lay-product in the direct air oxidation of cyclohexane to cyclohexanone.

Many processes have been developed for the neutralization of such acid containing streams. These include such methods as scrubbing the liquid to be neutralized with a liquid neutralizing material or contacting said liquid with a slurry of a neutralizing material. Both of these methods have disadvantages. In liquid treating processes the problem of entrainment is present and in the slurry type processes proper contacting of the liquid to be treated is always a problem because of diiculties in maintaining the slurry and subsequent ditiiculties in separating the slurry from the liquid being treated. Another method commonly used, and which has advantages over liquid-liquid methods or slurry type methods, is to pass the liquid which is to be treated over a xed bed of the neutralizing material. However, a major dil'liculty in the latter method is the formation of salts, resulting from the neutralizingreaction, which tend to coat the surface of the neutralizing material and destroy its neutralizing activity. This results in short runs because of shutdowns necessary to regenerate or replace the neutralizing material. Because of these short runs, such processes are not amenable to continuous operation for extended periods of time.

I have developed a process for neutralizing a liquid whereby the above difficulties are eliminated or at least mitigated. When operating according to my invention the surface of the neutralizing material is continuously revivied simultaneously with the neutralization reaction and the liquid being neutralized is given a nal concomitant wash, thereby removing any remaining traces of the contaminating material. e

Broadly speaking, my invention comprises. neutralizing-a stream of liquid by passing same over a bed of neutralizing material in the-presencefof a countercurrently llowing stream of water. Thus, the salts which form as a result of the neutralizing reaction are removed as they are formed and long continuous runs are made possible.

An object of this invention is to provide a process for neutralizing liquids.

Another object of this invention is to effect removal of acidic materials from liquids.

Another object of this invention is to continuously revivify the surface of a neutralizing material simultaneously with employing said material to neutralize a liquid.

Still another object of this invention is to prevent deposition of deactivating salts on the surface of a neutralizing agent, employed to neutralize acid containing liquids, by removing said salts as they are formed.

MStill another object of this invention is to provide a process for neutralizing a liquid by contacting said liquid with a neutralizing agent in the presence of a countercurrently flowing stream of water.

Other aspects, objects and advantages of the invention will be apparent, to those skilled in the art, from the acl companying disclosure and discussion.

Thus according to the invention there is provided a process for neutralizing acidic materials contained in an organic liquid which comprises contacting a stream of said liquid with a neutralizing material in the presence of a stream of water flowing countercurrently to said stream of liquid.

While the process of my invention can be used for neutralizing any acid containing organic liquid, it is particularly adapted for removing water insoluble acids,

whose salts, formed by the reaction of said acids with' the neutralizing material, are more water soluble thansaid acid. The only limitation on my process is a prac tical one, i. e., the salt formed must be sufciently water soluble that excessive quantities of water (from an ecoVV nomic standpoint) are not required to remove said salts from the surface of the neutralizing material. As a practical limit I have found that said salts should be solu ble at least to the extent of 0.5 gram per cc. of water, preferably to the extent of 1 gram per 100 cc. of water. Examples of acids which are substantially water insoluble and a salt thereof which is more soluble in water than the acid are:

Butyric acid 5.6 g./l00 g. H2O @D 5 C. Calcium butyrate 22.4 g./ 100 g. H2O 20 C. Adipic acid 1.5 g./l00 g. H2O 15 C. Calcium adipate 5.3 g./l00 g. H2O 15 C. Caproic acid 0.4 g./l00 g. H2O 20 C. Calcium caproate 2.18 g./ 100 g. H2O 20 C..

It is to be noted that the ater ows countercurrent to the stream of organic liquid which is being neutralized. Countercurrentilow is advantageous from several stand-- points. For example, when co-current flow is employed there is generally a greaterdispersion of the water in the organic liquid being treated and separationV of the:`

two phases is generally more troublesome than when counter-current flow is employed. Another advantage of countercurrent ow is that the organic liquid being treated is given a concomitant wash with water of ever increasingvpurity, and is linally' washed with substantially pure liquid is the continuo-us phasev only droplets of water Patented Oct. 7, 1958 Contact the neutralizing material and said water is less effective in removing said salts.

The attached drawing illustrates one form of apparatus which can be employed for carrying out the method of my invention. l l

Referring nnow to the drawing the invention will be more fully explained. Reference numeral designates a cylindrical, vertically disposed treatingchamber having therein a fixed bed of a neutralizing material 1 1 supported by a screen 12. While chamber 10 is illustrated asbeing vertically disposed it should beunderstood that horizontally disposed treating chambers can also be employed. Said chamber 10 is closed at its upper end by a closure member 13 attached thereto by'means of flange 14. While not shown in the drawing chamber 10 can be equipped with a similar closurev member at its lower end similarly attached to said lower end. A first conduit 15 extends into the lower portion of said chamber 10 and terminates in a distributor member 1K6, suitably supported by means not shown, and positioned beneath said screen 12. Positioned in said conduit 15 is a motor valve 17 operatively connected to rate of ow controller 18 which controls the rate of introduction of one liquid into chamber 10 through said conduit 15 by meansof pump 19. Extending into the upper portion of said chamberV 10 is a second conduit 20 having a motor valve 21 mounted therein. Motor valve 21 is operatively connected to rate of flow controller 22 which, controls the rate o f introduction of a second liquid into chamber 10 from tank 23 by means of pump 24. Liquid level controller 25 is mounted in the wall of chamber 10 and serves to control the level of the interface between said first and second liquids. While one type of level control is shown in the drawing it should be understood that other types of liquid level controllers can be employed. Liquid level controller 25 is operatively connected to rate of flow controller 22 and resets said rate of flow controller 22 responsive to the level of the interface between said first and second liquids in chamber 1l). Conduit 20 preferably extends below the level of said interface. A third conduit 26 extendsk from'the upper portion of said chamber 10 and serves as a withdrawal means for the less dense of said first and second liquids. A` fourth conduit 27 extends from a point below Vthe level of distributor 16 in the lower portion of chamber 10 and serves as withdrawal means for the more dense of said first and second liquids. Mounted within said conduit 27 Ais a motor valve 28 operatively connected to rate of flow controller 29 which controls the rate of withdrawal through conduit 27.

In operation, according to my presently preferred method of operation, column 10 is first filled with water to a point above the top of 'bed 11 but below the-level of conduit 26. Organic liquid containing acidic material is then introduced through conduit 15 and is dispersed as droplets by means of distributor 16 into the continuous water phasek in chamber 10. Said droplets bubble up through the water and form an upper phasewhich floats on said water. After formation of the upper phase the desired flow rates are established and the operation is on stream. The organic liquid passes up through the water, contacts the particles of neutralizing material 11 and the acidic. materials in said liquid are neutralized. As the organic liquid ows up the column it is contactedl countercurrently by the water flowing down thek column. Said water, being the continuous phase complet'ely surrounds the particles of neutralizing material and dissolves, as they are formed, salts which otherwise tend to, deposit on the. surface of the neutralizing material and destroy its activity. Thus the active surface of the neutralizing material is simultaneously revivified as the acidic materialsin the organic liquid are neutralized As said organic liquid continues to flow up the column itis concomitantly washed with the downflowing water. De-acidifiedvorganic liquid is withdrawn through conduit 26- and water is withdrawn through conduit 27.

Any suitable alkaline material can be used as the neutralizing material in the method of my invention. The neutralizing material employed should be substantially insoluble in water and unreactive with the organic liquid which is being treated. The terms water insoluble and insoluble in water as used herein and in the claims, as applied to the neutralizing material, means a material having a solubility in water less than 0.5 percent by weight, preferably less than 0.2 percent under the conditions employed. The actual choice of neutralizing material will depend upon the organic material being treated, the type of acid or contaminating material contained in said material, the amount of said acid present in said organic liquid, etc. as willr be understood by those skilled in the art. A presently preferred class of neutralizing materials are the basic compounds of the alkaline earth metals. Examples of which are, calcium hydroxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, strontium lcarbo-nate, etc. For eco-nomic reasons calcium carbonate is a presently preferred neutralizing material. Oyster shells, being approximately 97 percent calcium carbonate, are a convenient and economic source of calcium carbonate. Other forms of calcium carbonate such as limestone and marble can also be employed. As mentioned above the salt formed by the reaction between the acid and the neutralizing material should be appreciably soluble in water. For example, since calcium sulfate is soluble in water only to the extent of about 0.29 gram per 100 grams of water it would be preferable to employ a magnesium compound as the neutralizing material when one is neutralizing an organic liquid containing sulfuric. acid. The neutralizing material can be employed in lump, granular or powdered form. When using granular or powdered material the particle size can range from about l to 200 mesh. In most instances it is presently preferred to use a neutralizing material having a particle size of from l0 to 30 mesh. When employing crushedoyster shell asthe neutralizing material a convenient source of said oyster shell is that known. as chick grade in the poultry industry and which is commercially available.

The ow rate of the organic liquid being treated and the llow rate of the countercurrently flowing water through the treating chamber will depend upon the acid content and the desired degree of removal of said acid as will be understood by those skilled in the art. In counter-current operation, when operating with the water as a continuous phase, the water rate cannot be so great as to cause the organic liquid to be carried out the bottom of the treating chamber with said water. When neutralizing the oxidation eflluent from the air oxidation of cyclohexane to cyclohexanone, as described hereinafter, I have found that the water rate `can be conveniently maintained within 3 to 300 volumes per volume of neutralizing material per hour, preferably between 6 to 15.0 volumes per volume of neutralizing material per hour. With such water rates the organic liquid rate can be conveniently maintained within the range of 30 to 600 volumes per volume of neutralizing material per hour, preferably between 60 and 300 volumes per volume of neutralizing material per hour.

Any suitable temperature and pressure, depending upon the type of organic liquid being treated and the acid contained-therein, can be employed in carrying out my invention. Of course, it will be understood that the pressure should be such as to maintain said organic liquid and water in liquid phase.

Whilethe invention is described herein as applying to the neutralization of acids contained in the oxidation effluent from the air oxidation of cyclohexane to cyclohexanone, the invention can be employed for neutralizing any liquidrwhich is substantially iinmiscible with water. Iffthe liquid happens to be slightly soluble in water, the liquidwhich is dissolved in the water withdrawn from the treating chamber can be recovered by distillation. lIt is also apparent from the description of the invention given herein that the invention can be employed for neutralizing byproduct acids in the oxidation euent from any process wherein any type of hydrocarbon is oxidized to its primary oxidation products. Thus for example, the invention can be applied to the oxidation eiuent from the oxidation of alkanes and alkenes, including both alkyl and aryl alkanes and alkenes, as Well as to the oxidation eliluent of cycloparains and aryl compounds, including their substituted derivatives.. The term primary oxidation products is employed herein to include alcohols, ketones, hydroperoxides, peroxides, and other oxygenated derivatives of hydrocarbons. It does not include such products as carbon monoxide, carbon dioxide, water, etc. Examples of oxidation processes from which the oxidation eluent can be neutralized according to the invention include, among others, the oxidation of: alkanes such as pentanes, hexanes, octanes, decanes, etc., and alkyl derivatives thereof; alkenes such as pentenes, heptenes, octenes, decenes, etc., and alkyl derivatives thereof; naphthenes such as cyclopentane, methylcyclopentane, dimethylcyclopentane, methylethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, and diethylcyclohexane, etc.; naphthenyl cyclopentanes and cyclohexanes such as bicyclopentane, bicyclohexane, methylbicyclopentane, and methylbicyclohexane; etc.; hydroaromatics such as decahydronaphthalene, and methyldecahydronaphthalene etc.; olenic cyclic hydrocarbons such as cyclopentadiene, cyclohexadiene and alkyl substituted derivatives thereof etc.; alkenyl substituted cyclic hydrocarbons such as ethenylcyclopentane, ethenylcyclohexane, methylethenylcyclopentane, and dimethylethenylcyclohexane,'etc.; and aryl hydrocarbons such as benzene, toluene, etc.

It will be understood by those skilled in the art that the particular products obtained, i.' e., alcohols, ketones, peroxides, etc., will depend upon the hydrocarbon being oxidized, the reaction conditions etc. Any of the well known processes for the oxidation of hydrocarbons can be employed. For example, cyclohexane can be oxidized to cyclohexanone and cyclohexanol by blowing with air at a temperature of about 380 F., and a pressure of about 500 p. s. i. g., for a period of time, and in an amount suliicient to eiect the desired degree of oxidation.

When the process of the invention is carried out at elevated temperatures, particularly above about 100 C., peroxidic materials, particularly hydroperoxides, are decomposed.

Examples of organic liquids, not necessarily obtained by Voxidation of hydrocarbons, which can be neutralized according to my invention are: liquid hydrocarbons, saturated and unsaturated, cyclic and acyclic, aromatic, naphthenic and paranic; ethers, alcohols, aldehydes, ketones, heterocyclics etc.

As stated above, my invention is particularly adapted for removing from an organic liquid those acids which are only sparingly soluble or substantially insoluble in water. However, the invention can be employed to neutralize water soluble acids. With water soluble acids a simple water wash will be suicient in many instances. However, in those instances where disposal of the resulting acid water is a problem it is advantageous to employ my invention because, not only can a more ecient job of neutralizing be effected, but also said acid water is eliminated since it is not formed. For example, in neutralizing ka hydrocarbon containing sulfuric acid one would employ magnesium carbonate as the neutralizing material and the waste water would contain magnesium sulfate, not sulfuric acid as when only a simple water wash is employed.

The following examples will serve to explain the invention still more fully and to illustrate some of the advantages of the invention.

g. EXAMPLE I A one volume sample of the oxidation eiuent from the air oxidation of cyclohexane to cyclohexanone was passed by gravity flow over about two volumes of dry chick grade crushed oyster shell. Samples of the organic liquidwere analyzed for acid content before and after passage ,over said oyster shell. The acids Vin said organic liquid are believed to be a mixture of formic, acetic, caproic, butyric and adipic. The larger proportion of the acids was probably caproic acid. The results as shown in Table II below indicate the ineiectiveness of this method of neutralization since only about 31 percent of the acids in the organic liquid were removed.

EXAMPLE II The run of Example I was repeated except that said` oyster shell was first flushed with water. The water was drained and the organic liquid then passed over the wet oyster shell. The results shown in Table II below indicate an improvement over the method of Example I but also show that this method of neutralization is still ineicient.

EXAMPLE III hydroxide. Table I shows the results obtained in this method of neutralizing.

Table I Total Ilme Total Amt. Ml. 0.2 N Total Amt. of Slurry Added, Stirred, Water Base to grams minutes Added, ml. Neutralize 10 cc. Sample EXAMPLE IV A countercurrent neutralization apparatus, similar to that illustrated in the drawing, having 1200 volumes of chick grade crushed oyster shell therein was used for this run.- The column was iilled with water to a point above the top of the bed of said oyster shells. Organic liquid containing acidic material was introduced into the lower portion of the treating chamber through a suitabley distributor and allowed to bubble up through the water. An upper layer of organic liquid was established on top of the water layer, the desired ow rates were established with water flowing countercurrently to the organic liquid and the operation maintained continuously over a period of six hours. During said six hour period 7,150 volumes of the acid containing organic liquid was passed upwardly through the bed of oyster shells countercurrently to the downwardly owing stream of water. Samples of the treated organic liquid were withdrawn at frequent intervals and analyzed for acid content by titrating 10ml. of organic liquid with 0.2 N sodium hydroxide. The results of this method of neutralization are given in Table II belowwhich also presents a comparison of the results in all four of the above examples.

It can be seen from Table II that the countercurrentV continuous method of the present invention is about 100 percent better than the use of a slurry. The method of this invention is simpler in operation and more eiiicient inthe use ofthe CaCO3.

Various modifications of the invention can be made or carried out in the light of the above` disclosure without departing from the spirit or scope of said disclosure or the claims.

I claim:

1. In neutralizing an acid containing organic liquid wherein said liquid is contacted with a solid neutralizing agent insoluble in water and which reacts` with said acid to form salts which tend to coat the surface of said agentand thereby reduce its neutralizing activity, the method which comprises flowing a stream of water as a continuous phase through a fixed bed of said neutralizing agent and simultaneouslyv flowing said organic. liquid through said bed as a dispersed phase countercurrent to said stream of water.

2. A method for neutralizing acidic materials contained in a stream of liquid hydrocarbon which comprises:` continuously passing a stream of saidracid containing hydrof carbons upwardly as a dispersed phase through arv treating zone containing a iixed bed of a solid granular neutralizing material which is insoluble in water; continuously passing a stream of water as a continuous phaseV downwardly through` said treating zone; withdrawing treated hydrocarbon from the upper portion of said zone; and withdrawing water from the lower portion of said zone.

3. A method according to claim 2 whereinY said neutralizing material is crushed oyster shell.

4. In the neutralization of an acid containingV organic liquid wherein said liquid is contacted with a solid neu-v tralizing agent insoluble in water and which reacts with said acid to form salts which tend to coat the active'surface of said agent and thereby reduce its neutralizing activity, the method which comprises, passing said liquid upwardly as a dispersed phase through a bed of said neutralizing agent, simultaneously revivifying the active surface of said agent with a stream of water flowing as a continuous phase countercurrently to said stream of liquid,

and concomitantly and subsequently water washing said liquid.

5. In the neutralization of anacid containing organic liquid oxidation product obtained by the oxidation of a hydrocarbon to a primary oxidation product wherein said product is contacted with a solid neutralizing agent insoluble in water and which reacts with said acid to form salts which tend to coat the active surface of saidpagent and thereby reduce its neutralizing activity, the method which comprises, passing said product through a bed of said neutralizing agent, simultaneously revivifying the active surface of said agent with a stream of water flow-V ing countercurrently as a continuous phase to said stream of product flowing as a dispersed phase and concomitantly and subsequently water washing said product.

6; A method for neutralizing acidic materials contained in anorganic liquid streameiuent from theA air oxidation of cyclohexane to cyclohexanone which comprises: passing a stream of said liquid upwardly as a dispersed phase through a treating zone containing a fixed bed of crushed oyster shell at a rate within the range of 30 to 600 volumes per volume of oyster shell per hour; continuously passing a stream of water downwardly as a continuous phase throughsaid treating zone at a rate within the range of 3 to 300 volumes per volume of oyster shell; maintaining alevel of.v water above said bed; withdrawing treated organic liquid .from the. upper portion of said Zone at a point above said level of water; and withdrawing water from the lowerportioniof said zone.

7; Ina process for neutralizing an acid containing organic liquidi whereinv said liquid is passed through a fixed bedv ofV a solid: neutralizing agent insoluble in water and which reacts with saidc acid to form salts which tend to coat the surface of said agent and thereby reduce its neutralizing. activity, the improvement which comprises passing astream of water downward as a continuous phase through said bed of said neutralizing agent; simultaneously passing said organic liquid upward through said bed as a dispersed phase countercurrent to said stream of water with concomitant neutralization and water washing; and further washing treated organic liquid in a level of fresh water maintained. aboveV said bed.

8. In a process for the neutralization of an acid containing organic liquid wherein said liquid is contacted with a solid neutralizing agent insoluble in water and which agent reacts with said acid to form salts which tend to coat the surface of said agent and thereby reduce its neutralizing activity, the improved method of operation which comprises: introducing a stream of said liquid into the lower portion of ak treating zone containing a bed of said neutralizing agent; passing said liquid upwardly through said bed of neutralizing agent; introducing a stream of water into the upper portion of said treating zone above saidl bed of neutralizing agent; passing said water downwardly through said bed of neutralizing agent as aV continuous phase countercurrent to said stream of liquidy being passed upwardly as a dispersed phase so as torsimultaneously revivify the active surface of said neutralizing agent and concomitantly wash said upflowing liquid; maintaining a predetermined interfacial level of water` above the top of said bed; further washing said liquid in said level ofwater maintainedabove said bed; and controlling the amount of water introduced into said zone in accordance with the level of said water.

9. A method according` to claim 8 wherein said organicv References Cited in the file of this patent UNITED STATES PATENTS 48,367 Chesebrough J une 27, 1865 1,716,028 Canon June 4, 1929 1,952,622 Caldwell Mar. 27, 1934 1,968,397 Howes July 3l, 1934 2,552,670 Fleming May 15, 1951 2,609,395 Dougherty et al. Sept. 2, 1952 2,615,921 Dougherty et a1. ocr. 2s, 1952 OTHER REFERENCESy Pierre: Chem. Abst., vol. 24 (1930), p. 1920. 

1. IN NEUTRALIZING AN ACID CONTAINING ORGANIC LIQUID WHEREIN SAID LIQUID IS CONTACTED WITH A SOLID NEUTRALIZING AGENT INSOLUBLE IN WATER AND WHICH REACTS WITH SAID ACID TO FORM SALTS WHICH TEND TO COAT THE SURFACE OF SAID AGENT AND THEREBY REDUCE ITS NEUTRALIZING ACTIVITY, THE METHOD WHICH COMPRISES FLOWING A STREAM OF WATER AS A CONTINUOUS PHASE THROUGH A FIXED BED OF SAID NEUTRALIZING AGENT AND SIMULTANEOUSLY FLOWING SAID ORGANIC LIQUID THROUGH SAID BED AS A DISPERSED PHASE COUNTERCURRENT TO SAID STREAM OF WATER. 